Article

pubs.acs.org/est

Chemical Oxidation of Dissolved Organic Matter by Chlorine Dioxide,

Chlorine, And Ozone: Eects on Its Optical and Antioxidant
Properties
Jannis Wenk,,, Michael Aeschbacher, Elisabeth Salhi, Silvio Canonica, Urs von Gunten,,,,*
and Michael Sander,*

Eawag, Swiss Federal Institute of Aquatic Science and Technology CH-8600, Dubendorf, Switzerland
Institute of Biogeochemistry and Pollutant Dynamics, ETH Zurich, CH-8092, Zurich, Switzerland

School of Architecture, Civil and Environmental Engineering (ENAC), Ecole Polytechnique Federale de Lausanne (EPFL),
CH-1015 Lausanne, Switzerland

S Supporting Information
*

ABSTRACT: In water treatment dissolved organic matter

(DOM) is typically the major sink for chemical oxidants. The
resulting changes in DOM, such as its optical properties have
been measured to follow the oxidation processes. However,
such measurements contain only limited information on the
changes in the oxidation states of and the reactive moieties in
the DOM. In this study, we used mediated electrochemical
oxidation to quantify changes in the electron donating
capacities (EDCs), and hence the redox states, of three
dierent types of DOM during oxidation with chlorine dioxide
(ClO2), chlorine (as HOCl/OCl), and ozone (O3). Treatment with ClO2 and HOCl resulted in comparable and
prominent decreases in EDCs, while the UV light absorbances
of the DOM decreased only slightly. Conversely, ozonation resulted in only small decreases of the EDCs but pronounced
absorbance losses of the DOM. These results suggest that ClO2 and HOCl primarily reacted as oxidants by accepting electrons
from electron-rich phenolic and hydroquinone moieties in the DOM, while O3 reacted via electrophilic addition to aromatic
moieties, followed by ring cleavage. This study highlights the potential of combined EDC-UV measurements to monitor chemical
oxidation of DOM, to assess the nature of the reactive moieties and to study the underlying reaction pathways.

drinking waters.4,10,11 For these reasons, information on the

DOM concentration and its reactivity is indispensable to nd
the appropriate dose of an oxidant to meet the various
requirements of oxidative water treatment processes and to
avoid underperformance, higher costs, and undesired byproduct
formation during the oxidation step.
As a consequence, there is considerable interest in simple and
readily measurable parameters that provide information on the
concentration and reactivity of the DOM in the water.12,13 Two
commonly measured parameters are the dissolved organic
carbon (DOC) content, which captures the concentration of
DOM, and the specic UV absorbance of the water at the
wavelength of 254 nm (SUVA254, expressed in L mgC1 m1),
which is a proxy for DOM aromaticity.14 Previous work showed
that both the consumption of chemical oxidants by DOM and
the occurrence of some disinfection/oxidation byproducts are

INTRODUCTION
Drinking water and wastewater treatment facilities often have a
chemical oxidation step for disinfection, the removal of organic
micropollutants, color removal, and taste and odor control.
Among the most commonly used oxidants are chlorine dioxide
(ClO2), chlorine (as hypochlorous acid, HOCl and OCl), and
ozone (O3).1 For a number of reasons, the eciency of the
oxidation step and the quality of the treated water largely
depend on the reaction of the chemical oxidant with dissolved
organic matter (DOM). First, DOM is a major contributor to
drinking water color, which negatively aects the acceptance of
the water among consumers.2 Second, the reaction of DOM
with the chemical oxidants accelerates their consumption and,
thus, may reduce the eciency of the oxidation step for
disinfection and micropollutant oxidation.3,4 Third, the reaction
of the oxidants with DOM may result in the formation of
potentially harmful disinfection/oxidation byproducts.57
Fourth, chemical DOM oxidation results in the generation of
low molecular weight assimilable organic carbon (AOC).8,9
Following the oxidation step, the AOC needs to be removed by
biological ltration to improve the biological stability of
2013 American Chemical Society

Received:
Revised:
Accepted:
Published:
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August 22, 2013
August 26, 2013
August 26, 2013
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positively correlated to SUVA254.1519 These correlations

suggest activated aromatic moieties as major oxidizable
functional groups in DOM, consistent with the high reactivity
of low-molecular weight activated aromatic moieties, including
phenols, methoxybenzenes, and anilines, with ClO2, chlorine,
and O3.2029 However, despite the positive correlations with
chemical oxidant consumption, SUVA254 alone was found to be
a relatively poor predictor of DOM reactivity and disinfection
byproduct formation with chlorine.14,30 Other methods that
have been used to determine the concentration and reactivity of
oxidizable moieties in DOM are dicult to adapt for routine
water analysis or provide only indirect information on the redox
states of DOM.3137 Therefore, an analytical method is
desirable that allows for a direct quantication of changes in
DOM oxidation states caused by reaction with chemical
oxidants.38
Mediated electrochemical oxidation (MEO), an analytical
technique recently developed in our research group, fullls
these requirements. MEO allows for a fast and reliable
quantication of the electron donating capacities (EDCs)
(i.e., the number of electrons that are donated by a given
amount of DOM) of dilute DOM samples in electrochemical
cells with well-controlled pH and Eh conditions.39,40 We
previously demonstrated that MEO quanties activated
phenolic moieties in DOM: EDC values of a set of chemically
diverse humic substances (HS) were positively correlated with
their titrated phenol contents and showed dependencies on Eh
and pH comparable to those of low molecular weight phenols
and hydroquinones.40 We expect that chemical oxidants oxidize
these activated phenolic moieties in DOM, resulting in
decreasing EDC values of the DOM during treatment. MEO
may therefore be a powerful technique to quantify DOM
reactivity with chemical oxidants and to directly monitor
changes in DOM oxidation states during chemical oxidation in
water treatment.
The goal of this study was to explore the potential of
combined MEO and UVvisible absorbance measurements to
selectively quantify the oxidation states of DOM during
chemical oxidation and to elucidate the underlying oxidantdependent reaction pathways. We measured the UVvis
absorbance spectra and the EDC values of three HS (Suwannee
River Humic and Fulvic Acids (SRHA and SRFA) and Pony
Lake Fulvic Acid (PLFA)) during dose-dependent treatment
with ClO2, chlorine, and O3. HS, in general, make up the major
fraction of DOM. We specically chose SRHA, SRFA, and
PLFA because these materials are commercially available and
have been used in previous oxidation studies,18,41 and their key
physicochemical properties are known. Furthermore, SRHA/
FA and PLFA represent allochthonous and autochthonous
aquatic HS with terrestrial higher plant-derived and with
microbially derived precursor materials, respectively. This study
addresses fundamental questions on the changes in DOM
antioxidant properties and reactivities during chemical
oxidation, and, in the Implication section, highlights the
potential of combining MEO and SUVA254 measurements to
monitor chemical oxidant demand in water treatment facilities.

(NaClO3) (99%), ortho-phosphoric acid (85%), sodium

dihydrogen phosphate dihydrate (99%), disodium hydrogen
phosphate dodecahydrate (98.0%) and hypochlorite solution
614% were from Sigma-Aldrich, sodium dihydrogen phosphate monohydrate (99102%) was from Merck.
Humic Substances. Suwannee River Humic Acid Standard
II (SRHA; catalogue number: 2S101H), Suwannee River Fulvic
Acid Standard II (SRFA; 2S101F), and Pony Lake Fulvic Acid
Reference (PLFA; 1R109F) were obtained from the International Humic Substances Society (IHSS, St. Paul, MN) and
used as received. Selected physicochemical properties of the
HS, including elemental compositions, aromaticities and
titrated phenol contents, are provided in Table S1 in the
Supporting Information (SI).
Preparation of Aqueous Solutions. Aqueous solutions
were prepared using deionized water either from Milli-Q
(Millipore) or Barnsteadt water purication systems. HS stock
solutions (100 mg C L1) were prepared in 5 mM phosphate
buer (pH 8) or in deionized water. The DOC of the HS stock
solutions was determined after 25-fold dilution on a Shimadzu
V-CPH TOC analyzer (Kyoto, Japan) and used to calculate
specic UV absorbance values and carbon-normalized EDC
values.
Chlorine dioxide (ClO2) stock solutions (10 mM) were
produced by mixing potassium peroxodisulfate (K2S2O8, 2 g in
50 mL water) with sodium chlorite (NaClO2, 4 g in 50 mL).42
The stock solution of chlorine (Cl2; 10 mM) was prepared by
diluting a sodium hypochlorite solution with water. Ozone
(O3) stock solutions (1.3 to 1.5 mM) were prepared by
sparging ozone gas through water cooled in an ice bath.43 The
O3 gas was formed from pure oxygen with an Apaco CMG 33
ozone generator (Grellingen, Switzerland). The exact concentrations of oxidants in the stock solutions were quantied
spectrophotometrically using molar absorption coecients of
= 1200 M1 cm1 at = 359 nm for ClO2,44 = 350 M1 cm1
at = 290 nm for chlorine (as ClO),45 and = 3000 M1
cm1 at = 258 nm for ozone.46
ClO2, Chlorine, and O3 Oxidation of DOM. Oxidation
experiments were carried out in a series of identical glass
reaction vessels (50 or 100 mL) (Schott, Germany). The
vessels contained either DOM solutions (nominal concentrations of 0.83 mmol C L1 (=10 mg C L1) after reagent
mixing) or DOM-free blank solutions at pH 7 (50 mM
phosphate buer). Oxidant stock solutions were added to the
vessels under vigorous mixing on a magnetic stirrer plate. The
employed oxidant doses were in the range of 00.36 mmol
ClO2/mmol C, 00.85 mmol chlorine/mmol C, and 01.12
mmol O3/mmol C, which cover the ranges commonly used for
water treatment.28,47,48 Ozonation experiments were performed
in the presence (5 mM) and absence of t-BuOH as a scavenger
for formed hydroxyl radicals (OH). After oxidant addition, the
vessels were closed, removed from the stirrer and stored at 22
C for 12h for chlorine dioxide, 3 days for chlorine, and 2 h for
ozone. Subsequently, unreacted ClO2 and O3 were removed
from the solution by gently purging with helium for 20 min. In
selected experiments, residual chlorine (max. 0.5 M) was
measured using the DPD colorimetric method.42 The ozone
exposure in the DOM-containing systems in the presence and
absence of t-BuOH was measured according to previously
described methods.49,50 Control experiments in which t-BuOH
was added to the solutions after depletion of ozone showed that
t-BuOH did not aect UVvisible absorption and EDC
measurements.

MATERIALS AND METHODS

Chemicals. All chemicals were from commercial sources
and used as received: tert-butanol (t-BuOH) (99.7%), 2,2azino-bis(3-ethylbenzthiazoline-6-sulfonic acid) diammonium
salt (ABTS) (>99%), potassium peroxodisulfate (99%),
sodium chlorite (NaClO2) (puriss. p.a. 80%), sodium chlorate
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UV/Visible Light Absorbance Measurements. Absorbance spectra of untreated and oxidized HS were collected on
Uvikon 940 (Kontron Instruments) or Varian Cary 100
(Agilent Technologies) spectrophotometers in quartz glass
cuvettes (Hellma) (10 or 100 mm path lengths). All sample
spectra were corrected for the spectrum of the HS-free
phosphate buer (pH 7). The carbon-specic absorption
coecients of untreated and treated HS, a() [L/(mg Cm)],
were calculated according to eq 1, where A() is the sample
absorbance at a given wavelength , b [m] is the path length,
and CHS [mg C/L] is the organic carbon concentration of the
untreated HS.
a ( ) =

A ( )
bC HS

where I [A] is the baseline-corrected current and F (=96485 s

A/mole) is the Faraday constant, and mHS [mgC or mmolC ] is
the mass/amount of HS analyzed. Most HS samples were
analyzed in triplicates and some in duplicates with t = 50 min
between replicate analysis to ensure baseline-separation of
individual current peaks.

RESULTS AND DISCUSSION

Eects of Oxidant Treatments on DOM Optical
Properties. The specic absorption coecients of the
untreated samples decreased in the order SRHA>SRFA>PLFA
over the entire measured wavelength range from 220 to 600 nm
(SI Figures S1 and S2). The trend in the absorption coecients
follows the decrease in HS aromaticity55 from 31% for SRHA
to 22% for SRFA and 12% for PLFA (SI Table S1).56 The
absorbance spectrum of untreated SRHA extended further into
the red than the spectra of both SRFA and PLFA, which is
reected by the smaller S values for SRHA than for SRFA and
PLFA. Longer wavelength absorbance of HS has been ascribed
to charge transfer complexes between electron donor and
acceptor pairs in HS,55,57,58 which may be more abundant in
HA than FA.
Treatment of the HS with all oxidants resulted in decreasing
specic absorption coecients at all collected wavelengths
(Figure 1ac) and increasing S values (Figure 1df) with
increasing oxidant doses, consistent with previous reports.8,37,59,60 The absorbance spectra, the dierential spectra,
and the spectral slopes S275295 and S350385 of untreated and
oxidant-treated HS are shown in SI Figures S1S5. Overall, the
decreases in the specic absorption coecients suggest a
decrease in aromaticity of the treated HS. The increase in S
values with increasing oxidant dose indicates that moieties/
complexes absorbing at longer wavelengths were preferentially
removed and/or transformed into shorter wavelength-absorbing components. The increase in S and S275295 values with
increasing oxidant doses may also reect decreases in the
average molecular weights of the DOM upon reaction with the
chemical oxidants, as detailed in the SI. Consistent with
previous observations,30,61 the dierential spectra for HOCl
treated HS show a local maximum in absorption loss at around
270272 nm, indicating a selective removal of chromophores
in this wavelength region by reaction with chlorine under the
assumption that no new chromophores are formed. A similar
maximum loss in absorbance around 270 nm was also observed
for ClO2-treated PLFA. This feature was absent from the
dierential spectra of ClO2-treated SRHA and SRFA as well as
of the O3-treated SRHA, SRFA, and PLFA both in absence and
presence of t-BuOH.
A detailed analysis of the absorbance and dierential
absorbance spectra revealed that ClO2 and HOCl treatments
had dierent eects on DOM optical properties than the O3
treatments. The SUVA254 and SUVA280 values of all three HS
decreased linearly with increasing doses of ClO2 and HOCl and
followed similar dose-dependencies for the two oxidants
(Figure 1a-c and SI Figure S6, respectively). ClO2 and HOCl
treatment of SRHA and SRFA also resulted in comparable
increases in S with increasing oxidant doses, whereas PLFA
showed larger increases in S upon treatment with ClO2 than
HOCl at the same specic molar oxidant doses (Figure 1df).
In comparison to the ClO2 and HOCl treatments, ozonation
resulted in much larger decreases in the specic absorption
coecients of the HS, both in the absence and presence of tBuOH (Figure 1ac and SI Figure S6df). The larger

(1)

The values a(254 nm) and a(280 nm) are referred to as

SUVA254 and SUVA280, respectively. The spectral slope
coecients of the HS absorbance spectra, S [1/nm], were
obtained by nonlinear least-squares tting of DOM absorption
data from = 300 to 600 nm with a single exponential decay
function,51 where a(ref) is the specic absorption coecient at
the reference wavelength of ref = 350 nm.52
a() = a(ref ) exp[S ( ref )]

(2)

The parameter S describes the steepness of DOM absorbance

spectra on a logarithmic scale: The relative decrease in
absorbance with increasing wavelength becomes steeper as S
increases. Changes in the spectral slopes were also determined
over narrower wavelength ranges (i.e., from 275 to 295 nm,
S275295, and from 350 to 385 nm, S350385) following the
approach suggested by Helms and co-workers.53 Data tting
and integrations were performed using Origin 8.0 software
(OriginLab).
Quantication of Electron Donating Capacities. EDC
values of untreated and oxidant-treated HS solutions were
quantied by MEO using 2,2-azino-bis(3-ethylbenzthiazoline6-sulfonic acid) (ABTS) as electron transfer mediator.39,40
MEO measurements were conducted in an electrochemical cell
containing a reticulated vitreous carbon working electrode
(WE), a Pt counter electrode, and an Ag/AgCl reference
electrode. The electrochemical cells were rst lled with 6065
mL of buer solution (0.1 M KCl, 0.1 M phosphate, pH 7) and
the WE was polarized to an oxidizing potential of Eh = +0.725
V vs the standard hydrogen electrode (SHE), controlled by a
potentiostat (either an Autolab PG302 (EcoChemie B.V.) or a
630C instrument (CH Instruments)). A volume of 2 mL of an
aqueous ABTS solution (5 mM) was added to the cell, resulting
in an oxidative current peak due to the oxidation of ABTS to its
radical cation ABTS + (standard reduction potential
Eh0(ABTS+/ABTS) = 0.68 V vs SHE54). Upon attainment of
redox equilibrium between ABTS+/ABTS and the WE (and
hence stable current readings), HS samples (57 mL) were
successively spiked to the cell. Oxidation of electron donating
moieties in the added HS by ABTS+ resulted in the formation
of reduced ABTS, which was subsequently reoxidized at the
WE to ABTS+ to re-establish redox equilibrium. The resulting
oxidative current peak was integrated to yield the EDC values
of the added HS:

EDC =

FI dt
mHS

(Eq. 3)
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Figure 1. Changes in the optical properties of Suwannee River Humic Acid (SRHA), Suwannee River Fulvic Acid (SRFA), and Pony Lake Fulvic
Acid (PLFA) upon treatment with chlorine dioxide (ClO2), chlorine (as HOCl), and ozone (O3) (both in the absence and presence of t-BuOH).
Panels (a)-(c): Changes in the specic UV absorption at 254 nm (i.e., SUVA254) of (a) SRHA, (b) SRFA, and (c) PLFA as a function of the specic
molar oxidant dose (mmoloxidant (mmolc)1). Panels (d)(f): Changes in the spectral slope S (from 300 to 600 nm) of (d) SRHA, (e) SRFA, and (f)
PLFA as a function of the specic molar oxidant dose.

This can be explained by the higher content of ozone-reactive

chromophores in SRHA than in SRFA and PLFA. For SRFA
and PLFA, these moieties are depleted for specic ozone doses
>0.2 (mmolozone (mmolc)1) in the presence of t-BuOH, and
ozone-resistant SUVA254-contributing chromophores can then
only be further oxidized by OH, which are present during
ozonation in absence of t-BuOH.
Eects of Oxidant Treatments on DOM Antioxidant
Properties. In a rst set of experiments we evaluated the
sensitivity of MEO to detect oxidant-induced changes in the
EDCs of HS by quantifying the kinetics of PLFA oxidation by
O3 at a constant initial dose of 0.5 mmol O3/ mmol C. We
chose PLFA because it has the lowest EDC values of several
DOMs previously tested.40 Figure 2a shows the evolution of
the oxidative current responses in MEO for PLFA samples after
reaction with O3 for various reaction times. The corresponding
EDC values, obtained by integration of the oxidative current
peaks (Eq. 3), show fast oxidation of the electron donating
moieties in PLFA by O3 (Figure 2b): Within one minute and
12 minutes of reaction, the EDC of PLFA decreased to
approximately 50% and 15% of its original value, respectively.
The results of this experiment demonstrate the suitability of
MEO to quantify changes in the oxidation states of HS during
treatments with chemical oxidants. Based on the reaction
kinetics, the dose-dependent ozonation experiments were run
for 2 h to guarantee completion of HS-O3 reactions.
Figure 3 shows that the EDCs of SRHA, SRFA, and PLFA
decreased with increasing doses of ClO2, HOCl and O3 (both
in the presence and absence of t-BuOH) and, hence, dosedependent removal of electron donating moieties in the HS for

decreases in SUVA254 and SUVA280 upon treatment with O3

than ClO2 and HOCl at the same specic molar oxidant doses
demonstrates that UV-light absorbing aromatic moieties in the
HS were more eciently removed (or transformed to less
eciently absorbing moieties) by O3 than by both ClO2 and
HOCl. Note that narrower dose ranges were used for ClO2 and
HOCl than for O3 based on the eects of the three oxidants on
the antioxidant properties of the HS, as detailed below.
Ozonation in the presence of t-BuOH resulted in larger
losses in HS absorbance at wavelengths >315 nm and larger
increases in S than in the absence of t-BuOH. These eects of tBuOH can be ascribed to two factors. First, t-BuOH scavenges

OH which are formed by DOMozone reactions and which

catalytically degrade O3.16,62 Quenching of OH by t-BuOH
therefore enhanced O3 lifetimes and, hence, resulted in higher
O3 exposures of the HS. Enhanced O3 exposure in the presence
compared to the absence of t-BuOH was veried experimentally with PLFA solutions (see SI Figures S7, S8). Second,
by scavenging OH, t-BuOH shifted the overall oxidation
pathway from unselective, diusion-controlled OH additions,

H abstraction (and electron transfer reactions),62 to more

selective, direct reactions of O3 with moieties such as olens,
activated aromatics, and amines in the DOM.62 The presence of
t-BuOH therefore enhanced O3-reaction induced cleavage of
light absorbing olenic and aromatic systems,63 resulting in
larger changes in HS optical properties than in the absence of tBuOH. The abatement of SUVA254 by ozone (Figure 1ac)
was more ecient for SRHA in presence than in absence of tBuOH, whereas the opposite trend was observed for specic
ozone doses >0.2 (mmolozone (mmolc)1) for SRFA and PLFA.
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Figure 2. Ozonation of Pony Lake Fulvic Acid (PLFA). Eects of the reaction time on (a) the oxidative current responses in mediated
electrochemical oxidation (MEO) and (b) the corresponding electron donating capacities (EDC) of PLFA. Experimental conditions: 0.5 mmol O3/
mmol C; 5 mM t-butanol; 50 mM PO4-buer, pH 7.0. The samples were quenched with 1 mM maleic acid at selected reaction times.

of t-BuOH resulted in smaller decreases in SUVA254 and larger

decreases in the EDC values as compared to ozonation in the
absence of t-BuOH at the same initial ozone dose. We note that
the EDC measurements of PLFA samples at high O3 doses
were close to the quantication limit of MEO. The apparent
increase in the EDC value of PLFA at the highest O3 doses
(Figure 3c) therefore likely reected uncertainties in the EDC
quantication.
The eects on the optical and antioxidant properties of the
HS shown in Figure 4 can be rationalized on the basis of known
major reaction pathways of ClO2, HOCl, and O3 with lightabsorbing and electron donating phenolic moieties in the HS
(Figure 5). ClO2 reacts as a one-electron transfer oxidant with
low molecular weight phenols forming chlorite and the
corresponding phenoxyl radicals.21 At circumneutral pH, this
reaction proceeds mostly via the phenolate species because of
its oxidation rate constants with ClO2 that are about 6 orders of
magnitude higher than those for the nondissociated phenol
species.26 Analogously to low molecular weight phenols,
phenolic moieties in HS are expected to undergo one electron
oxidation by ClO2.
We have previously shown that HS contain electron donating
phenolic and hydroquinone moieties with apparent oxidation
potentials40,64 much lower than the standard reduction
potential of ClO2, Eh0(ClO2 (aq)/ClO2) = 0.954 V.65 SRHA
and SRFA are derived from higher-plant precursor materials,
including lignin, which is rich in methoxylated phenols.66
Generally, methoxylation activates phenols for electrophilic
attack and leads to faster oxidation kinetics.26 Phenoxyl radicals
resulting from a rst one electron oxidation26,67,68 may either
be further oxidized by reacting with another ClO2 to form
ortho- or para-quinones or undergo irreversible coupling
reactions. Hydroquinone moieties present in the untreated
HS are expected to be oxidized by ClO2 to semiquinone
intermediates and subsequently to the respective quinone
moieties. These reaction pathways involving ClO2 as the
oxidant have in common that electron donating phenolic
moieties are oxidized, whereas their UV-light absorbing
aromatic structure is preserved. In fact, based on the higher
molar absorption coecient of benzoquinone than hydroquinone at 254 nm, the oxidation of hydroquinone to quinone
moieties in the DOM may have resulted in higher SUVA254
values than measured if no hydroquinone moieties had been
oxidized. These pathways are therefore fully consistent with the

all three oxidants. Normalized to the same specic molar

oxidant dose, the decreases in EDC were largest for ClO2,
intermediate for HOCl and O3 in the presence of t-BuOH, and
smallest for O3 in the absence of t-BuOH: Linear ts of the
decreases in EDC values of SRHA and SRFA at low specic
molar oxidant doses had the steepest slopes for ClO2 (i.e.,
0.69 and 0.46 mmole(mmol ClO2)1), intermediate slopes
for HOCl (i.e., 0.38 and 0.36 mmole(mmol HOCl)1) and
for O3 in the presence of t-BuOH (i.e., 0.35 and 0.29
mmole(mmol O3)1), and the shallowest slopes for O3 in the
absence of t-BuOH (i.e., 0.15 and 0.08 mmole(mmol
O3)1) (SI Figure S9, Table S2)). The PLFA data did not show
a linear decrease in EDC with increasing specic molar oxidant
dose and could therefore not be tted.
Treatments with high doses of ClO2 and HOCl resulted in
complete loss of EDC in some of the systems, including a
replicate SRFA-ClO2 experiment (SI Figure S10), whereas all
HS retained some EDC during ozonation even at the highest
O3 doses. The removal of electron-donating moieties in the
tested HS was therefore more ecient by ClO2 and HOCl
treatments than by ozonation. The larger decreases in EDCs by
O3 in the presence than in the absence of t-BuOH can be
assigned to OH quenching by t-BuOH and hence higher O3
exposures of HS and more selective oxidations of electron
donating moieties by O3.
Mechanistic Interpretation. In the following, the changes
in the optical and the antioxidant properties of the HS will be
further explored by plotting the oxidant-induced decreases in
the SUVA254 values versus the corresponding decreases in the
EDC values (Figure 4). Treatments of the HS with ClO2 and
HOCl resulted in comparable SUVA254-EDC dependencies for
these two oxidants with larger relative decreases in the EDC
than in the SUVA254 values. This nding implies a more
ecient removal of electron donating phenolic moieties than
UV-light absorbing aromatic moieties upon treatment of the
HS with ClO2 and HOCl. Compared to the ClO2 and HOCl
treatments, ozonation in the presence and absence of t-BuOH
led to distinctly dierent SUVA254-EDC dependencies with
larger relative losses in the SUVA254 than in the EDC values.
Ozonation therefore caused a more ecient removal of UVlight absorbing aromatic moieties than electron donating
phenolic moieties. Ozonation of SRHA in the presence and
absence of t-BuOH resulted in comparable SUVA254-EDC
dependencies. Conversely, ozonation of SRFA in the presence
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Figure 3. Dependencies of the electron donating capacities (EDCs) of (a) Suwannee River Humic Acid (SRHA), (b) Suwannee River Fulvic Acid
(SRFA), and (c) Pony Lake Fulvic Acid (PLFA) on the specic molar doses of the chemical oxidants chlorine dioxide (ClO2), chlorine (as HOCl),
and ozone (in the absence and presence of t-BuOH).

Figure 4. Eect of chemical oxidant treatments on the specic UV absorbances (SUVA254) and the electron donating capacities (EDCs) of (a)
Suwanee River Humic Acid (SRHA), (b) Suwannee River Fulvic Acid (SRFA), and (c) Pony Lake Fulvic Acid (PLFA). The chemical oxidants used
were chlorine dioxide (ClO2), chlorine (as HOCl), and ozone (O3; in the absence and presence of tertiary butanol (t-BuOH)). The chemical oxidant
dose increased in the directions indicated by the grey arrows.

hydroxyphenols.72 This reaction pathway may therefore result

in similar changes in the optical and antioxidant properties as
ClO2, which acts almost exclusively by an electron transfer
mechanism.
The reaction of phenolic moieties with O3 at circumneutral
pH is dominated by phenolate and initiated by an ozone
adduct, which may react further by (i) loss of ozonide, O3, to
form a phenoxyl radical, (ii) loss of H2O2 to form an ortho
benzoquinone, (iii) loss of singlet oxygen, 1O2, to form a
catechol-type compound, and (iv) a Criegee-type reaction with
a cleavage of the aromatic ring.23,24,62 The formations of
phenoxyl radicals (pathway (i)) and catechols (pathway (ii))
are important but minor pathways for the oxidation of phenol
with ozone.23 If these would be the dominant reaction
pathways of phenolic moieties during ozonation, this would
lead to comparatively large decreases in the EDC and small
decreases in the SUVA254 values, whereas the opposite eect
was observed experimentally (Figure 4). Instead, the
pronounced decreases in SUVA254 support ring cleavage of
phenols and hydroquinones via the Criegee mechanism
(pathway (iv)) to form muconic-type compounds and
eventually aliphatic aldehydes (Figure 5). Ring cleavage
reactions may have involved nonphenolic aromatic moieties
such as anisoles and polymethoxybenzenes, as demonstrated for
low-molecular weight methoxylated compounds.22 The loss of
these moieties would have resulted in decreasing SUVA254
without aecting the EDC values of the HS, as both the target
compounds and products would not be oxidizable in MEO.

pronounced decreases in the EDC and the relatively small

losses in SUVA254 values observed for HS treatment with ClO2.
Phenolic moieties in HS may react with HOCl in an
electrophilic substitution reaction (Figure 5). At circumneutral
pH, this reaction proceeds via the phenolate due to its much
higher reactivity compared to the phenol.28 In this reaction,
HOCl attacks at the ortho and para positions to the hydroxyl
substituent, resulting in the formation of (poly)-chlorinated
phenols. Such an initial chlorination should not lead to a
decrease in the electron donating capacities of the phenolic
moieties.69,70 The reaction of low molecular weight phenols
with HOCl has been demonstrated to proceed via polychlorinated phenols which ultimately undergo ring cleavage to form
nonaromatic, chlorinated products (Figure 5).28 However, the
small changes in the SUVA254 values of HS upon HOCl
treatment do not support ring cleavage as a signicant reaction
pathway for phenolic, or more general, aromatic moieties
present in HS. Alternatively, the smaller relative decreases in
the SUVA254 than EDC values upon HOCl treatment are
consistent with the two-electron oxidation of hydroquinone
and/or catechol moieties by HOCl to form the respective
quinone moieties and chloride. These reactions are thermodynamically favorable given that the standard reduction potentials
for the two electron reductions of HOCl and OCl
(pKa(HOCl) = 7.54 at 25 C) (i.e., HOCl + H+ + 2e
Cl + H2O: Eh0 = 1.48 V71 and OCl + H2O + 2e Cl + 2
OH; Eh0 = 0.84 V71) are much higher than the oxidation
potentials of hydroquinones. This is in agreement with the high
second order rate constants for the reaction of HOCl with
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Figure 5. Proposed reaction pathways of phenolic moieties in the humic substances during reaction with chlorine dioxide (ClO2), chlorine (HOCl),
and ozone (O3).

IMPLICATIONS

identifying the major oxidant-dependent reaction pathways of

DOM.
In addition to advancing the fundamental understanding of
chemical DOM oxidation, the results from this study are also
relevant from a more applied, water treatment perspective.
MEO has potential to be used in water treatment facilities to
monitor DOM oxidation during a chemical oxidation step.
Combined determination of changes in the EDC and SUVA254
(or other suitable optical parameters) in close to real-time can
be used to control chemical oxidant doses. The resulting
rened dosing operation can minimize overdosing which may
have negative impacts on water quality, such as the enhanced
formation of disinfection/oxidation byproducts. Future work

This study establishes that the EDC of DOM is a parameter

that directly relates to the DOM redox state. The EDC is highly
sensitive to changes in DOM occurring during chemical
oxidation processes and can be readily quantied by mediated
electrochemical oxidation (MEO). If combined with measurements of complementary optical parameters, such as SUVA254,
the changes in the EDC values provide information on the
kinetics and the dose-dependent oxidation of electron donating
moieties in DOM. The combined analysis of optical and
antioxidant properties also provides insight into which moieties
in the DOM react with the chemical oxidants and helps
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needs to assess the potential of EDC-SUVA254 measurements as

a new tool to advance the understanding of and the capability
to predict other important processes occurring during chemical
oxidation of DOM, such as the formation of disinfection
byproducts, the generation of assimilable carbon, and the
eciency of disinfection.

ASSOCIATED CONTENT

S Supporting Information
*

Additional information as noted in the text. This material is

available free of charge via the Internet at http://pubs.acs.org.

AUTHOR INFORMATION

Corresponding Authors

*(U.v.G.) Phone: +41-(0)58 765 5270; fax: +41-(0)58 765

5210; e-mail: vongunten@eawag.ch.
*(M.S.) Phone: +41-(0)44 6328314; fax: +41 (0)44 633 1122;
e-mail: michael.sander@env.ethz.ch.
Present Address

(J.W.) Department of Civil & Environmental Engineering,

University of California at Berkeley, Berkeley, California 94720,
United States and ReNUWIt Engineering Research Center

Notes

The authors declare no competing nancial interest.

ACKNOWLEDGMENTS
J.W. and M.A. contributed equally to the work. This work was
supported by the Swiss National Science Foundation (Beitrage
200021-117911 and 200020-134801). We thank Marcel Burger
for help on measuring absorbance spectra and Hans-Ulrich
Laubscher for technical support.

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